New monoazo-dyestuffs



NEW MONOAZO-DYESTUFFS Henri Riat, Arlesheim, and Fritz Oesterlein, Basel, Switzerland, assignors to Ciba Limited, Basel, Switzerland,

a Swiss firm No Drawing. Application March 3, 1958 Serial No. 718,432

Claims priority, application Switzerland March 18,- 1957 5 Claims. (Cl. 260199) This invention provides valuable new monoazo-dyestuffs which are suitable for dyeing textile materials and correspond to the formula 2,906,748 Patented Sept. 29,1959

ICE

which can be obtained by the reduction of a dyestulf of the formula in which D and X have the meanings given above, is acylated with the anhydride or a halide of a p-halogenated propionic acid. 7, As such halides there may be mentioned principally the'chlorides of B-halogen-propionic acids such as fl-chlorop'ropionylchloride; i The acylation is advantageously carried out in the presence of an acid-containing agent, such as sodium acetate or sodium carbonate. It is carried out in'such manner that the aliphatically bound exchangeable'halo gen atom is present in the acylation product obtained, for example, by working in a weakly acid to neutral medium and/ or at as low a temperature as possible.

, Notwithstanding thepresence ofa labile halogen atom in the dyestuffs of the Formula 1' they can be isolated and by salting out and filtration.

which R represents a free amino group or the radical of an aliphatic alcohol of low molecular Weight bound through its oxygen atom.

The invention also provides a process for the manufacture of the monoazo-dyestuffs of the above Formula 1 wherein a coupling component of the formula is coupled with a diazo-compound of an amine of the formulain which A, D and the two Xs have the meaning given for Formula 1. a

As coupling component of the Formula 2 there may be used Z-ureido-8-hydroxynaphthalene-6-sulfonic acid and especially 2ureido-5-hydroxynaphthalene-7-sulfonic acid, and also Z-amino-5-hydroxynaphthalene-7-sulfonic acids of which the amino group is substituted by a carbalkoxy group of low molecular weight, for example a carbomethoxy or carbethoxy group or a group of the formula --COOC H --OCH As amines of the Formula 3 there may be mentioned more especially those which contain a sulfonic acid group in the benzene radical D, for example, 4-(fl-chloropropionylamino)-2-amino-benzene-1-sulfonic acid, 5-(fi-chlo ropropionylamino) -2-amino-benzene-l-sulfonic acid, S-(fibromopropionylamino)-2-amino-benzene-l sulfonic acid and 4-(fl-bromopropionylamino) 2-amino-benzene-1 sulfonic acid. 7 v

The coupling is advantageously carried out in an alkaline medium.

The invention also includes a modification of the process for making the dyestufis of the Formula 1, wherein an amino-monoaz o-dyestutf of the formula nmsx worked up into useful dry dyestufi preparations without losing their valuable properties. The dyestuffs are advantageously isolated at as low a temperature as possible The filtered dyestuffsjmay be dried, if desired, after the addition of an extender. The drying ispreferably carried out at nottoo high a temperature and under reduced pressure. In some cases dry preparations can be obtained by spray drying the whole mixture in which the dyestutf is prepared, that is to say, without first isolating the dyestuif. Y

These new dyestuffs of the Formula 1 are suitable for dyeing and printing a .very wide variety of materials such as leather, silk, Wool and superpoly'urethane and superpolyamide fibers, especially'polyhydroxylated fibrous materials, such as linen, regeneratedcellulose, and above all cotton, and also synthetic fibers of viscose. They are especially suitable for dyeing polyhydroxylated materials in the presence of alkali in an aqueous bath having a strong concentration of salt. Invcertain cases it is desirable, in order to improve exhaustion of the'bath or to obto subject the dyeings or prints so obtained to thorough rinsing with cold and hot water, if desired, with the addition of an agent having a dispersing action and assisting diffusion of any non-fixed dyestutf.

The dyeings produced with the new dyestutfson poly hydroxylated, especially cellulosic, fibers are generally'distinguished by the purity of their tints, by their good fast: mess to light, and above all by their excellent fastness to washing.

The following examples illustrate the invention, the

parts and percentages being by weight.

Example 1 27.8 parts of 4-(fl-ehloropropionylaminoi Z-aminobeng zene-l-sulfonic acid (obtained by the monoacylation of 2:4-diaminobenzene-l-sulfonic acid with fi-chloropropionylchloride) are stirred in 200 parts of water and 25 parts of concentrated hydrochloric acid and 25 parts'of a 4N.-

solution of sodium nitrite are added. When the diazotization is finished, the mixture is neutralized with 20 parts of sodium carbonate solution of 15% strength. The diazocompound is run into an ice-cold solution of 28.2 parts of 6-ureido-l-naphthol-3-sulfonic acid and 20 parts of sodium bicarbonate in 400 parts of water. When the coupling is finished, the partially precipiated dyestuff is completely salted out by the addition of sodium chloride, filtered off and dried in vacuo at 50-60 C. There is obtained an orange dyestutf which dyes cotton by the pro cess described in Example orange tints that are fast to washing.

A dyestufi having very similar properties is obtained by using, instead of 4-(fl-chloropropionylamino)-Z-aminobenzene-l-sulfonic acid, the equivalent quantity of 4-(5- brornopropionylamino) -2-aminobenzene-l-sulfonic acid.

By. using, instead of 6-ureido-1-naphthol-3-sulfonic acid, 7=ureido-1-naphthol-3-sulfonic acid, there is obtained a dyestufi which dyes cotton yellowish red tints.

Example 2 27.8 parts of 5-(B-chloropropionylamino)-2-aminoben Zene-l-sulfonic acid are diazotized in 200 parts oi water and 20 parts of hydrochloric acid with 6.9 parts of sodium nitrite. The diazo-compound is neutralized with sodium bicarbonate and coupled with a cold solution of o-ureido- 1-naphthol-3-Sulfonic acid and 20 parts of sodium bicarbonate. When the coupling is finished the dyestuff is 's'alted out, filtered off and dried. It dyes cotton pure scarlet tints having very good properties of wet fastness. It dyes wool from a weakly acetic acid bath pure scarlet tint's.

By using, instead of 6-ureido-l-naphthol 3-sulfonic acid, the equivalent quantity of 7-ureido-l-haphthol-3-sulfonic acid, there is obtained a dyestuff which dyes cotton red tints.

Example 3 27.8 parts of S-(fi-chloropropionylarnino)-2-amin0benzene-l-sulfonic acid are diazotized in 200 parts of water and 20 parts of concentrated hydrochloric acid with 6.9 parts of sodium nitrite. The diazo-compound is coupled with a solution of 32.1 parts of 2-carbethoxy-amino-5-hydroxynaphthalene-7-sulfonic acid rendered alkaline with sodium bicarbonate. When the coupling is finished the dyestutf is salted out, filtered ofl and dried. It dyes cotton fast pure scarlet tints.

A dystufi having similar properties is obtained by using, instead of Z-Carbethoxyamino-S-hydroxynaphthalene 7- sulfonic acid, 2-carbomethoxy-amino-S-hydroxynaphthalene-7-sulfonic acid, or the Z-carbethoxy-amino-S-hydroxynaphthalene-7-sulfonic acid whose ethoxy group bears a methoxy substituent in fi-position.

Example 4 20 parts of the amino-azo-dyestufif of the formula s odI HO Hols r m-004111,

(obtained by coupling diazotized S-nitro-Z-arnino-benzenel-sulfonic acid with 6-ureido-khydroxynaphthalene-B-sulionic acid followed by reduction of the nitro group to the amino group) are dissolved in 500 parts of water, and neutralized with sodium carbonate. There are then slowly added 20 parts of fl-bromoproprionyl chloride, and the reaction mixture is neutralized by the addition of a dilute solution of sodium hydroxide. The dyestuff is isolated by salting out, filtration and dryingin the usual manner, and dyescbudn pure scarlet tints.

Example 5 Z-pa'rtsof the dyestuff obtained as described in the first paragraph of Example 1 are dissolved in 100 parts of water. The cotton fabric is impregnated with the resulting solution on a foulard and the fabric is squeezed to remove the excess liquid and retain on the material of its weight of dyestufi solution. The material so impregnated is dried, and then impregnated at room temperature in a solution containing, per liter, 10 grams of sodium hydroxide and 300 grams of sodium chloride, then squeezed to a weight increase of 75% and steamed for 60 seconds at IOU-101 C. The material is then rinsed, treated in a sodium bicarbonate solution of 0.5% strentgh, rinsed, soaked for a quarter of an hour in a solution of 0.3% strength of a non-ionic detergent at the boil, then rinsed and dried. There is obtained a pure orange dyeing which is fixed fast to boiling.

What is claimed is:

1. A monoazo-dyestuff which in its free acid state corresponds to the formula A-HN ' N=N -x sotn X Cl-GHzCHrC ONH SOJH NH-C 0--R wherein R represents a lower alkoxy group.

3. A monoazo-dyestufi whieh in its free acid state corresponds to the formula soiH wherein one X is hydrogen and the other a substituent of the formula NHCO Nl-I 4. The monoazo-dyestufi which in its free acid state corresponds to the formula 5. The monoazo-dyestufi which in its free acid state corresponds to the formula f r-cmem-w-HN Ems 1 fnereincs at... a treat or as has.

UNITED STATES PATENTS 1,731,643 Wagner et a1. Oct. 15, 1929 2,384,750 Knight et al. Sept. 11, 1945 ,752 Knight et a1. Sept. 11, 1945 2,384,753 Knight Sept. 11, 1945 

1. A MONOAZO-DYESTUFF WHCIH IN ITS FREE ACID STATE CORRESPONDS TO THE FORMULA 